An Efficient Diastereoselective Reduction of α‐Alkyl‐β‐keto Carbonitriles with TiCl4/BH3 or LiBH4/CeCl3 to syn‐ or anti‐α‐Alkyl‐β‐hydroxy Carbonitriles
Identifieur interne : 001721 ( Istex/Corpus ); précédent : 001720; suivant : 001722An Efficient Diastereoselective Reduction of α‐Alkyl‐β‐keto Carbonitriles with TiCl4/BH3 or LiBH4/CeCl3 to syn‐ or anti‐α‐Alkyl‐β‐hydroxy Carbonitriles
Auteurs : Renato Dalpozzo ; Giuseppe Bartoli ; Marcella Bosco ; Antonio De Nino ; Antonio Procopio ; Letizia Sambri ; Antonio TagarelliSource :
- European Journal of Organic Chemistry [ 1434-193X ] ; 2001-08.
English descriptors
- KwdEn :
- Amino alcohols, Carbonitriles, Carbonyl function, Cdcl3, Chem, Chloride molar ratio, Complete reduction, Conformation, Crude mixture, Cyano, Cyano group, Dalpozzo, Diastereoisomeric mixtures, Diastereoisomeric ratio, Dihedral angle, Dramatic decrease, Electronic repulsions, Eluent light ether, Flash column chromatography, Full paper, Functionalized ketones, Hydroxy carbonitriles, Isomer, Keto, Keto carbonitrile, Keto carbonitriles, Keto phosphane, Large variety, Lewis acid, Libh4, Minor isomer, More peaks, Nitrile function, Orthogonal position, Other hand, Phenyl frameworks, Pure diastereoisomers, Pure diastereomeric mixture, Reaction times, Room temperature, Stereochemical outcome, Steric interactions.
- Teeft :
- Amino alcohols, Carbonitriles, Carbonyl function, Cdcl3, Chem, Chloride molar ratio, Complete reduction, Conformation, Crude mixture, Cyano, Cyano group, Dalpozzo, Diastereoisomeric mixtures, Diastereoisomeric ratio, Dihedral angle, Dramatic decrease, Electronic repulsions, Eluent light ether, Flash column chromatography, Full paper, Functionalized ketones, Hydroxy carbonitriles, Isomer, Keto, Keto carbonitrile, Keto carbonitriles, Keto phosphane, Large variety, Lewis acid, Libh4, Minor isomer, More peaks, Nitrile function, Orthogonal position, Other hand, Phenyl frameworks, Pure diastereoisomers, Pure diastereomeric mixture, Reaction times, Room temperature, Stereochemical outcome, Steric interactions.
Abstract
α‐Alkyl‐β‐keto carbonitriles can be reduced stereoselectively to syn‐ and anti‐α‐alkyl‐β‐hydroxy carbonitriles. The stereoselectivity can be explained in terms of properties of the Lewis acid employed. TiCl4 in noncoordinating solvents such as dichloromethane, followed by reduction with the borane/pyridine complex, predominantly led to the syn‐α‐alkyl‐β‐hydroxy carbonitriles, according to a chelate transition state, whereas CeCl3 in coordinating solvents such as THF, followed by reduction with LiBH4, predominantly led to the anti‐isomers, in agreement with an open‐chain transition state. The reduction to syn‐α‐alkyl‐β‐hydroxy carbonitriles is the first general preparation of these compounds.
Url:
DOI: 10.1002/1099-0690(200108)2001:15<2971::AID-EJOC2971>3.0.CO;2-K
Links to Exploration step
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<front><div type="abstract" xml:lang="en">α‐Alkyl‐β‐keto carbonitriles can be reduced stereoselectively to syn‐ and anti‐α‐alkyl‐β‐hydroxy carbonitriles. The stereoselectivity can be explained in terms of properties of the Lewis acid employed. TiCl4 in noncoordinating solvents such as dichloromethane, followed by reduction with the borane/pyridine complex, predominantly led to the syn‐α‐alkyl‐β‐hydroxy carbonitriles, according to a chelate transition state, whereas CeCl3 in coordinating solvents such as THF, followed by reduction with LiBH4, predominantly led to the anti‐isomers, in agreement with an open‐chain transition state. The reduction to syn‐α‐alkyl‐β‐hydroxy carbonitriles is the first general preparation of these compounds.</div>
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<abstract>α‐Alkyl‐β‐keto carbonitriles can be reduced stereoselectively to syn‐ and anti‐α‐alkyl‐β‐hydroxy carbonitriles. The stereoselectivity can be explained in terms of properties of the Lewis acid employed. TiCl4 in noncoordinating solvents such as dichloromethane, followed by reduction with the borane/pyridine complex, predominantly led to the syn‐α‐alkyl‐β‐hydroxy carbonitriles, according to a chelate transition state, whereas CeCl3 in coordinating solvents such as THF, followed by reduction with LiBH4, predominantly led to the anti‐isomers, in agreement with an open‐chain transition state. The reduction to syn‐α‐alkyl‐β‐hydroxy carbonitriles is the first general preparation of these compounds.</abstract>
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